Method of in-situ hydrogenation of carbonaceous material

Abstract

In-situ hydrogenation of an underground coal formation is carried out by fracturing the formation and sealing it, to provide an in-situ reactor site. Then a liquid solvent stream and a gaseous hydrogen stream are introduced into the fractured formation, allowing reaction and conversion of the coal to lighter, hydrogenated components.

I claim: 
     
       1. A process for the recovery of carbonaceous materials from an underground formation by in-situ hydrogenation, comprising: (a) drilling a bore hole into an underground formation containing carbonaceous material and placing concentric pipes in said bore hole for the addition and withdrawal of materials,   (b) fracturing a portion of the formation containing carbonaceous material surrounding the bore hole,   (c) sealing off said underground formation around said pipes to form the equivalent of a pressure reactor in the formation below the seal,   (d) introducing a preheated liquid solvent stream and a preheated gaseous stream comprising hydrogen through the bore hole into said fractured formation,   (e) contacting the carbonaceous material in said fractured formation with said preheated solvent and said preheated hydrogen to produce a product mixture comprising at least a partially hydrogenated carbonaceous material, and   (f) removing said product mixture from said fractured formation.   
     
     
       2. The process of claim 1 wherein said product mixture comprises, in addition, dissolved carbonaceous material. 
     
     
       3. The process of claim 1 wherein the carbonaceous material is selected from the group consisting of coal, oil shale, tar sands, and heavy crudes. 
     
     
       4. The process of claim 1 wherein the pressure in the in-situ formation is maintained at from about 200 psi to about 2000 psi. 
     
     
       5. The process of claim 1 wherein the temperature in the in-situ formation is maintained at from about 500° F. to about 900° F. 
     
     
       6. The process of claim 1 wherein at least a portion of the liquid stream is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F. 
     
     
       7. The process of claim 1 wherein at least a portion of the liquid stream is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, with a boiling range of from about 650° to about 975° F. 
     
     
       8. The process of claim 1 wherein the gaseous stream is at least about 50 volume percent hydrogen. 
     
     
       9. The process of claim 1 comprising, in addition, separating, fractionating, and hydrocracking said product mixture to provide a product comprising a 975° F. product fraction, and using said product fraction as feed for a hydrogen producing plant. 
     
     
       10. The process of claim 1 wherein the preheated liquid stream and the preheated gaseous stream are mixed prior to contacting the underground carbonaceous material. 
     
     
       11. The process of claim 1 comprising, in addition, removing a portion of said fractured formation prior to contacting said carbonaceous material in-situ in said fractured formation with said preheated liquid solvent and said preheated gas comprising hydrogen. 
     
     
       12. A process for the recovery of carbonaceous materials from an underground formation by in-situ hydrogenation, comprising: (a) drilling a bore hole into an underground formation containing carbonaceous material selected from the group consisting of coal, oil shale, tar sands, and heavy crudes, and placing concentric pipes in said bore hole for the addition and withdrawal of materials,   (b) fracturing a portion of the formation containing carbonaceous materials surrounding the bore hole,   (c) sealing off said underground formation around said pipes to form the equivalent of a pressure reactor in the formation below the seal,   (d) maintaining said underground formation at a pressure of from about 200 psi to about 2000 psi and at a temperature within a range of from about 500° F. to about 900° F.,   (e) introducing (1) a preheated liquid solvent stream, wherein at least a portion of the liquid stream is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen and having a boiling range of from about 650° to about 975° F. and wherein at least a portion of the liquid stream is a hydrocarbon-containing liquid having a boiling range of from about 300° to about 1200° F., and   (2) a preheated gaseous stream comprising at least about 50 volume percent hydrogen, into the deposit through the bore hole,     (f) contacting the carbonaceous material in said fractured formation with said preheated solvent and said preheated hydrogen to produce a product mixture comprising at least a partially hydrogenated carbonaceous material and dissolved carbonaceous material, and   (g) removing said product mixture from said fractured formation.   
     
     
       13. The process of claim 12, comprising, in addition, separating, fractionating, and hydrocracking said product mixture to provide a product comprising a 975° F. +  product fraction, and using said product fraction as feed for a hydrogen producing plant. 
     
     
       14. A process for the recovery of carbonaceous materials from an underground formation comprising: (a) drilling a bore hole into an underground formation containing carbonaceous material and placing concentric pipes in said bore hole for the addition and withdrawal of materials,   (b) sealing off said underground formation around said pipes to form the equivalent of a pressure reactor in the formation below the seal,   (c) introducing a preheated liquid solvent stream and a preheated gaseous stream comprising hydrogen into the deposit through the bore hole,   (d) contacting the carbonaceous material in the formation with said preheated liquid solvent stream and said preheated gaseous stream to produce a product mixture comprising at least a partially hydrogenated carbonaceous material, and   (e) removing said product mixture from said formation.   
     
     
       15. The process of claim 14 wherein said product mixture comprises, in addition, dissolved carbonaceous material. 
     
     
       16. The process of claim 14 wherein the carbonaceous material is selected from the group consisting of tar sands and heavy crudes. 
     
     
       17. The process of claim 14 wherein the pressure in the in-situ formation is maintained at from about 200 psi to about 2000 psi. 
     
     
       18. The process of claim 14 wherein the temperature in the in-situ formation is maintained within a range of from about 500° F. to about 900° F. 
     
     
       19. The process of claim 14 wherein at least a portion of a liquid stream is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F. 
     
     
       20. The process of claim 14 wherein at least a portion of the liquid stream is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, and having a boiling range of from about 650° to about 975° F. 
     
     
       21. The process of claim 14 wherein the gaseous stream is at least about 50 volume percent hydrogen. 
     
     
       22. The process for the recovery of carbonaceous materials selected from the group consisting of tar sands and heavy crudes, from an underground formation, comprising: (a) drilling a bore hole into an underground formation containing carbonaceous material and placing concentric pipes in said bore hole for the addition and withdrawal of materials,   (b) sealing off said underground formation around said pipes to form the equivalent of a pressure reactor in the formation below the seal,   (c) introducing (1) a preheated liquid solvent stream, wherein at least a portion of said stream is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F., and further wherein at least a portion of said stream is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen and having a boiling range of from about 650° F. to about 975° F., and   (2) a preheated gaseous stream comprising at least about 50 volume percent hydrogen, into the deposit through the bore hole, and wherein the equivalent reactor has a pressure maintained at from about 200 to about 2000 psi and further has a temperature maintained within the range of from about 500° F. to about 900° F.,     (d) contacting the carbonaceous material in the formation with said preheated liquid solvent stream and said preheated gaseous stream to produce a product mixture comprising at least a partially hydrogenated carbonaceous material and dissolved carbonaceous material, and   (e) removing said product mixture from said formation.   
     
     
       23. The process of claim 22, comprising in addition separating, fractionating and hydrocracking said mixture to provide, among other products, a product comprising a 975° F. +  product fraction, and using said product fraction as a feed for a hydrogen producing plant. 
     
     
       24. A process for the recovery of carbonaceous materials from an underground formation comprising: (a) contacting carbonaceous material in-situ in an underground formation with preheated liquid solvent and a preheated gas comprising hydrogen to produce a product mixture comprising at least a partially hydrogenated carbonaceous material and dissolved carbonaceous material, and   (b) removing said product mixture from said formation.   
     
     
       25. The process of claim 24 wherein the carbonaceous material is selected from the group consisting of tar sands and heavy crudes. 
     
     
       26. The process of claim 24 wherein the pressure in said underground formation is maintained at from about 200 psi to about 2000 psi. 
     
     
       27. The process of claim 24 wherein the temperature in said underground formation is maintained at from about 500° F. to about 900° F. 
     
     
       28. The process of claim 24 wherein at least a portion of the liquid solvent is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F. 
     
     
       29. The process of claim 24 wherein at least a portion of the liquid solvent is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, and having a boiling range of about 650°-975° F. 
     
     
       30. The process of claim 24 wherein at least about 50 volume percent of said preheated gas comprises hydrogen. 
     
     
       31. A process for the recovery of carbonaceous materials from an underground formation comprising: 
     
     
       (a) contacting carbonaceous material selected from the group consisting of tar sands and heavy crudes in-situ in an underground formation with (1) a preheated liquid solvent, wherein at least a portion of said liquid is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F. and further wherein at least a portion of said liquid is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, and having a boiling range of from about 650° F. to about 975° F., and   (2) a preheated gas comprising at least about 50 volume percent hydrogen, and wherein the temperature in said underground formation is maintained in the range of from about 500° F. to about 900° F. and wherein the pressure is maintained at from about 200 psi to about 2000 psi, to produce a product mixture comprising at least partially hydrogenated carbonaceous material and dissolved carbonaceous material, and     (b) removing said product mixture from the formation.   
     
     
       32. A process for the recovery of carbonaceous materials from an underground formation, comprising: (a) fracturing a portion of an underground formation, comprising carbonaceous material,   (b) contacting the carbonaceous material in-situ in said fractured formation with preheated liquid solvent and a preheated gas comprising hydrogen to produce a product mixture of at least a partially hydrogenated carbonaceous material and dissolved material, and   (c) removing said product mixture from said formation.   
     
     
       33. The process of claim 32 comprising, in addition, removing a portion of said fractured formation prior to contacting said carbonaceous material in-situ in said fractured formation with said preheated liquid solvent and said preheated gas comprising hydrogen. 
     
     
       34. The process of claim 32 wherein the carbonaceous material is selected from the group consisting of coal, oil sale, tar sands, and heavy crudes. 
     
     
       35. The process of claim 32 wherein the pressure in the in-situ formation is maintained at from about 200 psi to about 2000 psi. 
     
     
       36. The process of claim 32 wherein the temperature in the in-situ formation is maintained within a range of from about 500° F. to about 900° F. 
     
     
       37. The process of claim 32 wherein at least a portion of the liquid stream is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F. 
     
     
       38. The process of claim 32 wherein at least a portion of the liquid stream is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, and having a boiling range of from about 650° F. to about 975° F. 
     
     
       39. The process of claim 32 wherein at least about 50 volume percent of said gas comprises hydrogen. 
     
     
       40. A process for the recovery of carbonaceous materials from an underground formation, comprising: (a) fracturing a portion of an underground formation, comprising carbonaceous material selected from the group consisting of coal, oil shale, tar sands, and heavy crudes,   
     
     
       (b) contacting the carbonaceous material in-situ in the fractured formation with (1) a preheated liquid solvent, wherein at least a portion of the liquid is a hydrocarbon-containing liquid having a boiling range of from about 300° F. to about 1200° F., and further wherein at least a portion of the liquid is a hydrocarbonaceous liquid having the property of donating and accepting hydrogen, and having a boiling range of from about 650° F. to about 975° F., and   (2) a preheated gas comprising at least 50 volume percent hydrogen, and wherein the pressure in the fractured formation is maintained at from about 200 psi to about 2000 psi, and the temperature is maintained at from about 500° F. to about 900° F., to produce a product mixture of at least a partially hydrogenated carbonaceous material and dissolved carbonaceous material, and     (c) removing said product mixture from said formation.   
     
     
       41. The process of claim 40 comprising, in addition, removing a portion of said fractured formation prior to contacting said carbonaceous material in-situ in said fractured formation with said preheated liquid solvent and said preheated gas comprising hydrogen.